Combination additive for gasoline



. knock characteristics of the fuels.

United States Patent Delaware No Drawing. Filed July 16, 1962, Ser. No. 210,232 Claims. or. 44-69) V This invention relates in general to improved motor fuels, and particularly to leaded gasolines containing a multifunctional additive which enhances the octane quality of the gasoline.

'It is well known that organolead compounds are added to most modern gasolines in order to improve the anti- However, the octane increment obtained by the use of increasing amounts of lead antiknock additive has diminished as the amounts of aromatic and olefinic components employed in modern gasolines have increased. 1 :;It is alsowell known that various phosphorus compounds are utilized in gasoline to serve as deposit modifiers. However, the compounds commonly employed often seriously degrade the octane quality of the gasoline. Thus, more lead antiknock additive must be added in order to counterbalance the octane degradation caused byithe phosphorus compound. However, since it takes a" large amount of the lead compound to enhance the octane quality of modern fuels, and since there are health limitations on the amount of lead compounds that can be utilized in gasoline, a problem exists in the industry.

Thus, it is an objectof this invention to provide multifunctional additiveswhichenhance the octane quality of ferred to' as ketenes'wherein the carbon atom of the carbonyl group is directly attached'to an adjacent ethylenically bonded carbon atom. These ketenes may be represented by the'formula: I

C=C=O Rs wherein R and R are organic radicals selected from the group consisting of aromatic, aliphatic and alicyclic radicals and hydrogen.

" Suitable ketenes ofvthis invention included aliphatic aldoand ketoketenes wherein R and R are selected from the group consisting of alkyl radicals of from 1 to 6 carbon atoms and hydrogen. Such ketenes included di- 7 methyl ketene, diethyl ketene, dicyclohexyl ketene, methyl cyclohexyl ketene, ethyl phenyl ketene, and the like.

Ketenes can be prepared by well-known methods, e.g., from a halogen acyl halides by theaction of zinc, as set forth in Die Ketene by H. Staudinger, Stuttgart, 1912.] Ketene, the preferred agent of this invention, can be prepared by the pyrolysis offacetone or aceticacid vapor at about 600 to 750 C. The thermal decomposition of 1 mol of acetic acid yie'ldsyl mol of ketene and 1 mol. of water. The pyrolysisof 1 mol of acetone yields 1 mol of ketene and l molqof methane. The latter method is generally preferred since the methane acts as an inert carrier for the ketene.

The anhydrous acids of phosphoruswhich are suitablefor this invention include the monobasic hypophosphorus acid, H PO phosphorus acid, H PO which usually exists in the dibasic form but may exist in the tribasic form,

ICC

the tribasic orthophosphoric acid, H PO and the tetrabasic hypophosphoric acid, H P O and pyrophosphoric acid, 114F207.

The preferred acid is anhydrous orthophosphoric acid, H PO The commercial preparations of this acid are Well known.

The amount of ketene to be utilized in this invention will depend upon whether the acid of phosphorus is monobasic, dibasic, tribasic or tetrabasic. In general, the agent should be employed within the range of from 0.8 to 1.1 mols of ketene for each mol of hydroxyl in the acid of phosphorus. A range of 0.95 to 1.05 mols is preferred. The reaction temperature is not critical, but is generally within a range of from 40 to F.

In preparing the preferred additive of this invention, gaseous ketene is bubbled by means of a sparger into dry H PO It is desirable to continue the reaction until about three mols of ketene have reacted with each mol of H PO The reaction can also be accomplished by contacting the gaseous ketene and the anhydrous H P0 in a packed tower.

The fuels in which the additives of this invention are useful are conventional leaded gasolines used in internal combustion engines. Such gasolines generally boil between 80 and 450 F. Their octane numbers, as determined by ASTM Method D-908, range from about 83 to or higher. The additives are particularly useful in gasolines having an octane number above 95. Lead compounds, such as tetraethyl lead, tetramethyl lead, and tetravinyl lead, are generally employed in concentrations of from about 0.5 to 7 cc./ga1.

The additives of this invention are advantageously employed in minor amounts sufiicient to enhance the octane quality of a leaded gasoline. Said minor amountsare generally in the range of from about 0.05 to 2% by volume'based on the gasoline blend, and preferably in the range of from about 0.1 to 1% by volume.

The following examples illustrate the efi'icacy and unobvious nature of this invention.

EXAMPLE 1 Reid vapor pressure j 7.3 Saturates, volume percentage 67.3 Olefins, volume percentage 11.7

Aromatics, volume percentage 21.0- Percentage evaporated: 1

-158 F. 23.5 212 F. 45.9 257 F. 77.0 '302 F. 97:3 Tetraethyl lead, cc./gal 1.96 Research Octane-Number 102.7 Motor-Octane Number I 94.1

Laboratory octane ratings of the Research OctaneNumher and the Motor Octane Number were obtained using the Direct Match Method.

The RON of the gasoline was determined by the Standard ASTM Research Method Test Procedure D-908-5 1,

Which is described in the 1952 edition of ASTM Man .ual of Engine Test Methods for Rating Fuels. The MON was determined by the Standard ASTM Motorv Method Test Procedure'D-357, which is. explained in the 'ketene, treated phosphates did not enhance the octane 1953 edition of ASTM Manual of Engine Test Methods 7 "quality of the leaded gasoline. i Q I for Rating Fuels. V In summary, it is seen-that the instant invention is The improved octane quality. of the fuel can'be as'cer-'- limited .to products obtained by-.re acting various ke- .tained byireference to the datain Table V I. 5 tenes with acidsjof phosphorus, and that closely related 'Volmne Percent Additive RON A Ron" M N" I mixture of monoalkyl and .dialkyl phosphateswereadded c 4 H products arenot-eifective. w i -I b I What isclimd is?" a 1. A leaded ga'soline containing a minor amount suffifcient to enhance the octane quality .of'the gasoline .of

the reaction productsobtained by reacting with an or- 1"'ganic1ketenewhich hasthe structural formula:

r *Rl 7 I The above data clearly demonstratethe lJe1 1efic1a1.. If] vvhiei einiR andR are organicradicals selected from the c yfi m x mqv 1 f fil m t group consisting-of hydrogen and alkyl radicals of from additives to 'a'leadedgasohne. f a 1 1 to.-.6.'carbon atoms,

EX MPLE 1 :].2Q"saidl'organiciketene isketene. Y other tests P a compounds closely'mlat'id 3f A-leade"d. motorfuel according to claim liwherein' the i ds 1 Ph P F d n t Wha "said minorfamount-of reaction productsiis fromaODSitQ the octane; qualityv of; leaded gasol1nes.-.-E 1;65 g. .of

peli mol of hydroxyl in the acidof 'pho s'pho ius bein'gwith to. 1840 cc. ofaleade'd. gasolinein orderto determine'thej: -m Offmm 0.310111. V

effect of the mixture-on the'octane"quality 'of the gaso i 'Tahl'eIL- Alkyl grouns are'CaOxo. t Averaged idirect mat hdeter minations. I

' tane quality of the-fuel. -Moreover; treatingtheiphbis- 1- l e .m g iF' -l 'l at wi T' i rangecontaining.from. O;05 to '2 %fbyvolume of 'the 3, Qf' h? s fliq miq s F f -1 -4Q 9 inoductsobtained by .r eacting H PO;Withmketene in a of the sam s ne nd s s as; srf ii i rdt I ratio of mm 0.8 10511 mm of ketene p eramol bf hyto determine the eflect ofthe ketene treated phosphates-g30 b H3170? r on the c u l r u -i h s q ap sag n;

5..=.A leaded mot'oi'lfuel ccording to-claim;4vkherein' 's aidmatio is'trd 019510.101, i

Sept. 12, 1961' These data show that' the phosphates degrade (lithe ce 7 ignition, Proceedings of American Petroleum! Institute,

' 1. 2. A"leadedmotor fuel accord nglto i laim l' wherein' 2% bywohime; and-'therratioi qf-fmols' of organic ketene V T 4;;1A leaded moto fuel boiling nthe' gas olifnfeboilin g June 14;, 195.7

zjstrkaayr stu yo lAdditivestoReduce rife- Patent No. 3,167,410 January 26 1965 Robert W. Malone It is hereby certified that error a ent req'liring correction and that t corrected below.

ppears in the above numbered pathe said Letters Patent should read as Column 4, line 10, after "reacting" insert H PO Signed and sealed this 6th day of July 1965.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER A 1 testing Officer Commissioner of Patents 

1. A LEADED GASOLINE CONTAINING A MINOR AMOUNT SUFFICIENT TO ENHANCE THE OCTANE QUALITY OF THE GASOLINE OF THE REACTION PRODUCTS OBTAINED BY REACTING WITH AN ORGANIC KETENE WHICH HAS THE STRUCTURAL FORMULA: R1-C(-R2)=C=O WHEREIN R1 AND R2 ARE ORGANIC RADICALS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND ALKYL RADICALS OF FROM 1 TO 6 CARBON ATOMS. 